Ion Jelly: a tailor-made conducting material for smart ... · Ion Jelly: a tailor-made conducting material for smart electrochemical devices† Pedro Vidinha a* , Nuno M.T. Lourenço
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S1
Supporting information for:
Ion Jelly: a tailor-made conducting material for smart
electrochemical devices†
Pedro Vidinhaa*, Nuno M.T. Lourençoab, Carlos Pinheiroa, Ana R. Brása, Tânia Carvalhoa, Teresa S. Silvaa, Abhik Mukhopadhyaya, Maria J. Romãoa, Jorge Parolaa, Madalena Dionisioa, Joaquim M.S.Cabralb, Carlos A.M.
Afonsoc & Susana Barreirosa*
aREQUIMTE/CQFB, Departamento de Química, FCT, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal, bIBB - Institute
for Biotechnology and Bioengineering, Av. Rovisco Pais, 1, 1049-001, Lisboa, Portugal and cIN- Institute of Nanoscience and Nanotechnology, Av. Rovisco Pais, 1, 1049-001, Lisboa, Portugal.
*Address correspondence to Pedro Vidinha or Susana Barreiros phone no. 351 21 2949681
Contents Materials and Methods S2 Pictures of ion jelly materials S4 Ion jelly synthesis table S5 X-ray diffraction patterns S7 Differential scanning calorimetry analysis S8 Conductivity of ion jelly films S9 In situ spectroelectrochemical cycling data for Glass – ITO/PEDOT/ion jelly/PB/ITO – Glass S12 Ion jelly wire S13
Materials and Methods All ionic liquids based on the imidazolium cation and were provided by Solchemar. The tri-n-octyl-methylammonium chloride (Aliquat 336®) ionic liquid was provided by Sigma-Aldrich. 1-ethyl-3-methylimidazolium-2-(2-methoxyethoxy)ethylsulfate [emim][MDEGSO4] - ECOENG™21M was provided by Solvent Innovation. ITO glass was obtained from ICE. Gelatin (Cultimed, Panreac), K3[Fe(CN)6 (Aldrich, ACS reagent, ≥99.0%) FeCl3.6H2O (Riedel-de Haën, puriss. p.a., ≥99%), HCl (Panreac reagent grade), KCl (Merk), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate (PEDOT/PSS, Aldrich conductive grade) were used as received.
N N
H
HHN N
R2
R1
Prussian Blue (PB) film preparation PB films were electrogenerated on glass indium tin oxide transparent electrode. The electrochemical polymerization was performed in a conventional three-electrode cell. An aqueous solution of 5 mM K3[Fe(CN)6, 5 mM FeCl3.6H2O, 5 mM HCl and 0.2 M KCl was used as PB polymerization solution. Electropolymerization conditions: constant applied voltage of 0.55nV (vs. Ag/AgCl), for 300 s. After deposition, the electrode was gently rinsed with distilled water. Electrochromic Window Assembly The electrochromic window set-up was constructed using two ITO glasses, each one covered with a different electrochromic layer, of PB and of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate (PEDOT/PPS), respectively. The ion jelly was spread over PEDOT/ITO using a pipette, forming a homogenous film. The film was left to jellify before being covered with PB/ITO. The window was then sealed with epoxy glue. Electrochemical and spectroscopic measurements Electrochemical polymerization and choronocoulometry/chronoabsorptometry were performed with a conventional three-electrode cell using a computer controlled computerized potentiostat-galvanostat Model 12 Autolab, from Eco-Chemie Inc. The collection of data was controlled by GPES Version 4.9 Eco Chemie B.V. Software (Utrecht, The Netherlands). Working electrode: PEDOT/ITO. The PB/ITO electrode functioned both as auxiliary and reference electrode. UV/Vis absorbance chronoabsorptometry spectra were recorded in a Shimadzu UV2501-PC spectrophotometer. All spectroscopic measurements of the electrochromic cell were done in situ. Conductivity measurements The conductivity of several ion jelly films was measured using an impedance analyzer (Alpha-N Analyzer from Novocontrol GmbH), covering a frequency range from 0.1 Hz to 1 MHz. Films were placed between two gold-plated electrodes (diameter 20 mm) of a parallel plate capacitor. The temperature control, with a precision of ± 0.1 K, was assured by the QUATRO Cryosystem also supplied by Novocontrol GmbH. Frequency dependent ionic conductivity of the different gel films was measured from -110 to 40ºC.
X-ray diffraction The X-ray diffraction measurements were carried out on a Enraf-Nonious X-ray generator equipped with a Cu-Rotating anode. The diffraction patterns were collected, by rotating the sample 360° with a step size of 1° and an exposure time of 1h, with a detector to sample distance of 90 mm. General ion jelly synthesis 100-300 μL of ionic liquid was heated to 40 ºC and under magnetic stirring 1 equivalent mass of gelatin was added. The amount of added water depended on the hydrophilicity and initial water content of the ionic liquid used, as measured through Karl-Fischer titration. In the case of water-miscible ionic liquids, a water content of 10 % was used, whereas non water-miscible ionic liquids were used water-saturated. The mixture was kept stirring at 40 ºC until gelatin was completely solubilized (1 to 24 hours). The solution was then spread over a glass surface or used to fill a mold. Jellification occurred at room temperature. “R” indicates ionic liquid/gelatin mass ratio (w/w). Different types of material formed are shown in Figure S1.
Figure S1- Type of material formed upon combining an IL with gelatin. (a) - solid transparent block of [bmim] [(CN)2N] R(IL/gelatin )=3; (b) - solid transparent film of [emim] [EtSO4]; (c) - solid rigid block of [bmim] [BF4].
[S1] -Yoshida, Y., Baba, O., Larriba, C. , Saito G. (2007), J. Phys. Chem. B ,111, 12204. [S2] - Sigma-Aldrich ionic liquids
Figure S4 - Conductivity spectra of ion jelly films at -60ºC [bmim][N(CN)2](R=3); [bmim][N(CN)2](R=1); [bmim][Cl](R=1); [Him][Cl](R=1); [C10mim][Cl](R=1); [Hmim][Cl](R=1); [emim][EtSO4](R=1); R=mIL/mgelatin.
In situ spectroelectrochemical cycling data for Glass – ITO/PEDOT/ion jelly/PB/ITO – Glass, ion jelly wire Figure S9 – In situ spectroelectrochemical cycling data for Glass-ITO/PEDOT/ion jelly/PB/ITO-Glass. A - Chronoabsorptometry recorded at 700nm; B - Square-wave switching between -1V (step duration 60 s) and +1, V (step duration 60 s) (vs. PB);